Patent GB-1081825-A (GB)
Title: Metal derivatives of dialkylhydroxyphenylalkylphosphonic acids and phosphonic acid half-esters
IPC: C07F9/02
Filed: 1966-01-13
Abstract: Various organic materials are stabilized by incorporating therein compounds of formula (I) [P]mMx[G]p wherein M is a metal or a metal alkyl having an available valence of from 1-4; G is an anion having an available valence of from 1-3 and P is of the formula <FORM:1081825/C4-C5/1> and wherein z is 0-6, y is 1-4, n is 0-1, m is 1-3, x is 1-2, p is 0-3, n, m, p, and x being selected so as to satisfy the expression <FORM:1081825/C4-C5/2> wherein r is the valence of the anion G.  The group M consists either of a metal in full free valence state such as sodium, cadmium, zinc, barium, nickel, aluminium, tin, chromium, cobalt, iron, copper and titanium, or of a metal derivative in which part but not all of its full free valance state is satisfied by alkyl substitution, e.g. dialkyl tin. Materials which may be stabilized include lubricating oils of the aliphatic ester type, animal and vegetable oils, such as linseed oil, fat, tallow, lard, cod liver oil, castor oil, palm oil and cotton seed oil, hydrocarbons such as gasoline, diesel oil, mineral oil, fuel oil, cutting fluids, waxes, and resins; fatty acids, varnishes and soaps.  Example 32 describes the stabilization of gasoline, lard, an aliphatic ester lubricating oil and paraffin wax using a compound of formula shown above.ALSO:Polymeric materials are stabilized and/or dyed in the presence of a dye by incorporating therein compounds of formula <FORM:1081825/C3/1> wherein M is a metal or a metal alkyl having an available valence of from 1-4; G is an anion having an available valence of from 1-3 and P is of the formula <FORM:1081825/C3/2> and wherein z is 0-6, y is 1-4, n is 0-1, m is 1-3, x is 1-2, p is 0-3, n, m, p, and x being selected so as to satisfy the expression <FORM:1081825/C3/3> The group M consists either of a metal in full free valence state such as sodium, cadmium, zinc, barium, nickel, aluminium, tin, chromium, cobalt, iron, copper and titanium, or of a metal derivative in which part but not all of its full free valence state is satisfied by alkyl substitution, e.g. dialkyl tin. Polymers which may be stabilized or dyed using the above compounds include polyolefines, vinyl resins formed from the polymerization of vinyl halides or from the copolymerization of vinyl halides with unsaturated polymerizable compounds, e.g. vinyl esters, a , b -unsaturated acids, esters, ketones or aldehydes, and unsaturated hydrocarbons, polyurethanes, polyamides, polyesters, polycarbonates, polyacetals, polystyrene, polyethylene oxide, polyacrylics and also mixtures of the above. Examples 23-25 and 27 describe compositions of polypropylene containing various stabilizers of formula shown, which are tested for stabilization against oxidation, thermal decomposition, and degradation by light; Example 26 describes the dyeing of polypropylene containing as dyesites various compounds of formula shown, and Examples 28-31 describe the stabilization of polyethylene, nylon-6-polyamide, polyvinyl chloride, and an acrylonitrile-butadiene-styrene terpolymer with compounds of formula shown.ALSO:The invention comprises compounds of formula <FORM:1081825/C2/1> wherein M is a metal or a metal alkyl having an available valence of from 1-4; G is an anion having an available valence of from 1-3 and P is of the formula <FORM:1081825/C2/2> and wherein z is 0-6, y is 1-4, n is 0-1, m is 1-3, x is 1-2, p is 0-3, n, m, p and x being selected so as to satisfy the expression <FORM:1081825/C2/3> The group M consists either of a metal in full free valence state such as sodium, cadmium, zinc, barium, nickel, aluminium, tin, chromium, cobalt, iron, copper and titanium, or of a metal derivative in which part but not all of its full free valence state is satisfied by alkyl substitution e.g. dialkyl tin.  They are prepared by reaction of an appropriate phosphonic acid or half ester of formula <FORM:1081825/C2/4> wherein Z is hydrogen or alkyl, with the appropriate metal derivative.  When preparing the mixed salts of the invention a stoichiometric excess of the metal derivative is used and it is especially convenient to use a double decomposition reaction between an easily prepared salt of compounds of Formula (III) and the appropriate metal derivative.  The compounds are useful as stabilizers and dyesiters for organic materials.  Example 1(a) describes the preparation of 2,6 - di - t - butyl - 4 chloromethyl phenol by reaction of 2,6-Di-t-butyl phenol with hydrogen chloride and paraformaldehyde, and Example 2(b) that of 2,6-Di-t-butyl-4-(b -chloroethyl) phenol by the action of thionyl chloride on 2,6-di - t - butyl - 4 - (b  - hydroxyethyl) phenol. These methods are also applicable to the preparation of other specified dialkyl chloroalkyl phenols.  Examples 1(b) and 2(c) describe the preparations of Di - (n - butyl) 3,5 - di - t - butyl - 4-hydroxybenzyl - and di - (n - dodecyl) - b -(3,5 - di - t - butyl - 4 - hydroxyphenyl) ethylphosphonates by the action of the tri-(n-alkyl)-phosphite on the appropriate dialkyl-chloroalkyl phenol.  Example 2(a) describes the preparation of 2,6 - di - t - butyl - 4 - (b  - hydroxyethyl) phenol by the action of lithium aluminium hydride on methyl 3,5 - di - t - butyl - 4 - hydroxyphenylacetate.  Example 3 describes the preparation of 3,5di - t - butyl - 4 - hydroxybenzylphosphonic acid by refluxing diphenyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate with potassium hydroxide.